EP2144975B1 - Liquid- crystalline medium - Google Patents
Liquid- crystalline medium Download PDFInfo
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- EP2144975B1 EP2144975B1 EP08758588A EP08758588A EP2144975B1 EP 2144975 B1 EP2144975 B1 EP 2144975B1 EP 08758588 A EP08758588 A EP 08758588A EP 08758588 A EP08758588 A EP 08758588A EP 2144975 B1 EP2144975 B1 EP 2144975B1
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- compounds
- liquid
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- crystalline medium
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- 0 *C1COC(C(Cc(c2c3F)cc(*)c3F)C2(F)F)OC1 Chemical compound *C1COC(C(Cc(c2c3F)cc(*)c3F)C2(F)F)OC1 0.000 description 19
- PLPCCGGCRQVLPC-UHFFFAOYSA-N CC(CC1)CCC1C(CC1)CCC1c1ccc(-c(cc2F)cc(F)c2F)c(F)c1 Chemical compound CC(CC1)CCC1C(CC1)CCC1c1ccc(-c(cc2F)cc(F)c2F)c(F)c1 PLPCCGGCRQVLPC-UHFFFAOYSA-N 0.000 description 1
- PGMXDMWOPNAPDX-UHFFFAOYSA-N CC(CC1)CCC1c(cc1)ccc1C(C1=[F])=CC=C(C)C1F Chemical compound CC(CC1)CCC1c(cc1)ccc1C(C1=[F])=CC=C(C)C1F PGMXDMWOPNAPDX-UHFFFAOYSA-N 0.000 description 1
- DGCDLQDRPCFWSL-UHFFFAOYSA-N CC1CNC(C(CC2)CCC2F)NC1 Chemical compound CC1CNC(C(CC2)CCC2F)NC1 DGCDLQDRPCFWSL-UHFFFAOYSA-N 0.000 description 1
- QUMMJTIKNXWJOA-UHFFFAOYSA-N CC1CNC(c(cc2)ccc2F)NC1 Chemical compound CC1CNC(c(cc2)ccc2F)NC1 QUMMJTIKNXWJOA-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/0403—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems
- C09K2019/0407—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems containing a carbocyclic ring, e.g. dicyano-benzene, chlorofluoro-benzene or cyclohexanone
Definitions
- the invention relates to a liquid-crystalline medium based on a mixture of polar compounds having negative dielectric anisotropy ( ⁇ ), which contains at least one compound selected from the group of compounds of the formula I, IIA and IIB and at least one compound of the formula I* in which
- Media of this type are to be used, in particular, for electro-optical displays with active-matrix addressing based on the ECB effect, for IPS (in plane switching) and for FFS (fringe field switching) displays.
- LC phases which can be used industrially are required to have a liquid-crystalline mesophase in a suitable temperature range and low viscosity.
- None of the series of compounds having a liquid-crystalline mesophase that have been disclosed hitherto includes a single compound which meets all these requirements. Mixtures of two to 25, preferably three to 18, compounds are therefore generally prepared in order to obtain substances which can be used as LC phases. However, it has not been possible to prepare optimum phases easily in this manner, since no liquid-crystal materials having significantly negative dielectric anisotropy and adequate long-term stability have hitherto been available.
- Matrix liquid-crystal displays are known.
- Non-linear elements which can be used for individual switching of the individual pixels are, for example, active elements (i.e. transistors).
- active matrix is then used, where a distinction can be made between two types:
- the electro-optical effect used is usually dynamic scattering or the guest-host effect.
- the use of single-crystal silicon as substrate material restricts the display size, since even modular assembly of various part-displays results in problems at the joins.
- the electro-optical effect used is usually the TN effect.
- TFTs comprising compound semiconductors, such as, for example, CdSe, or TFTs based on polycrystalline or amorphous silicon.
- CdSe compound semiconductors
- TFTs based on polycrystalline or amorphous silicon The latter technology is being worked on intensively worldwide.
- the TFT matrix is applied to the inside of one glass plate of the display, while the other glass plate carries the transparent counterelectrode on its inside. Compared with the size of the pixel electrode, the TFT is very small and has virtually no adverse effect on the image.
- This technology can also be extended to fully colour-compatible displays, in which a mosaic of red, green and blue filters is arranged in such a way that a filter element is opposite each switchable pixel.
- the TFT displays disclosed hitherto usually operate as TN cells with crossed polarisers in transmission and are back-lit.
- MLC displays of this type are particularly suitable for TV applications (for example pocket TVs) or for high-information displays in automobile or aircraft construction.
- TV applications for example pocket TVs
- high-information displays in automobile or aircraft construction Besides problems regarding the angle dependence of the contrast and the response times, difficulties also arise in MLC displays due to insufficiently high specific resistance of the liquid-crystal mixtures [ TOGASHI, S., SEKIGUCHI, K., TANABE, H., YAMAMOTO, E., SORIMACHI, K., TAJIMA, E., WATANABE, H., SHIMIZU, H., Proc. Eurodisplay 84, Sept. 1984: A 210-288 Matrix LCD Controlled by Double Stage Diode Rings, pp. 141 ff., Par is; STROMER, M., Proc.
- the disadvantage of the MLC-TN displays disclosed hitherto is due to their comparatively low contrast, the relatively high viewing-angle dependence and the difficulty of producing grey shades in these displays.
- the invention has the object of providing MLC displays which are based on the ECB, IPS or FFS effect and do not have the disadvantages indicated above, or only do so to a lesser extent, and at the same time have very high specific resistance values.
- the invention thus relates to a liquid-crystalline medium having negative dielectric anisotropy which contains at least one compound selected from the group of compounds of the formula I, IIA and IIB and at least one compound of the formula I*.
- the mixtures according to the invention exhibit very favourable values for the capacitive threshold, relatively high values for the holding ratio and at the same time very good low-temperature stability as well as very low rotational viscosities.
- Liquid-crystalline medium contains one or more, preferably 1, 2 or 3, compound(s) of the formulae I and one or more, preferably one, compound(s) of the formula I*.
- R 1 is preferably alkyl; m is preferably 1; Z' is preferably a single bond.
- R 0 is preferably H.
- a 1 is preferably a 1,4-cyclohexenylene or 1,4-cyclohexylene radical, in which one or two non-adjacent CH 2 groups may be replaced by -O-.
- Liquid-crystalline medium contains one or more compounds of the formula IIA and/or IIB and one or more, preferably one, compound(s) of the formula I*.
- X 1 is preferably F or Cl and X 2 is preferably F.
- Liquid-crystalline medium which additionally contains one or more compounds of the formula III in which
- the invention furthermore relates to an electro-optical display with active-matrix addressing based on the ECB effect, characterised in that it contains, as dielectric, a liquid-crystalline medium according to one of Claims 1 to 16.
- the liquid-crystal mixture preferably has a nematic phase range of at least 60 K and a flow viscosity ⁇ 20 of at most 30 mm 2 ⁇ s -1 at 20°C.
- the liquid-crystal mixture according to the invention has a ⁇ of -0.5 to -8.0, preferably -2.0 to -7.0, in particular -3.0 to -6.0, where ⁇ denotes the dielectric anisotropy.
- the rotational viscosity ⁇ 1 is preferably ⁇ 150 mPa ⁇ s, in particular ⁇ 140 mPa ⁇ s.
- the birefringence ⁇ n in the liquid-crystal mixture is generally between 0.07 and 0.16, preferably between 0.08 and 0.11.
- the mixtures according to the invention are suitable for all VA-TFT applications, such as, for example, MVA, PVA and ASV. They are furthermore suitable for PS-VA (Polymer stabilized VA), IPS, FFS and PALC applications with negative ⁇ .
- PS-VA Polymer stabilized VA
- IPS Polymer stabilized VA
- FFS FFS
- PALC PALC
- the nematic liquid-crystal mixtures in the displays according to the invention generally comprise two components A and B, which themselves consist of one or more individual compounds.
- Component A has significantly negative dielectric anisotropy and gives the nematic phase a dielectric anisotropy of ⁇ -0.3. It preferably comprises compounds of the formulae I, IIA and/or IIB.
- the proportion of component A is preferably between 45 and 100 %, in particular between 60 and 100 %.
- one (or more) individual compound(s) which has (have) a value of ⁇ of s -0.8 is (are) preferably selected. This value must be more negative the smaller the proportion A in the mixture as a whole.
- Component B has pronounced nematogeneity and a flow viscosity of not greater than 30 mm 2 ⁇ s -1 , preferably not greater than 25 mm 2 ⁇ s -1 , at 20°C.
- Particularly preferred individual compounds in component B are extremely low-viscosity nematic liquid crystals having a flow viscosity of not greater than 18 mm 2 ⁇ s -1 , preferably not greater than 12 mm 2 ⁇ s -1 , at 20°C.
- Component B is monotropically or enantiotropically nematic, has in most cases no smectic phases and is able to prevent the occurrence of smectic phases down to very low temperatures in liquid-crystal mixtures. Some compounds of Component B have smectic phases but their solubility are usually good. For example, if various materials of high nematogeneity are added to a smectic liquid-crystal mixture, the nematogeneity of these materials can be compared through the degree of suppression of smectic phases that is achieved.
- Preferred compounds of the formulae V and VI are given in the following table for example CCP-V-m, CCP-Vn-m, CCP-nOm, CCP-nm, BCH-nm.
- liquid-crystal phases may also comprise more than 18 components, preferably 18 to 25 components.
- the phases preferably comprise 4 to 15, in particular 5 to 12, compounds of the formulae I, IIA and/or IIB and optionally compounds of the formulae III-VI, preferably compounds of the formula III and V.
- the other constituents are preferably selected from nematic or nematogenic substances, in particular known substances, from the classes of the azoxybenzenes, benzylideneanilines, biphenyls, terphenyls, phenyl or cyclohexyl benzoates, phenyl or cyclohexyl cyclohexanecarboxylates, phenylcyclohexanes, cyclohexylbiphenyls, cyclohexylcyclohexanes, cyclohexylnaphthalenes, 1,4-biscyclohexylbiphenyls or cyclohexylpyrimidines, phenyl- or cyclohexyldioxanes, optionally halogenated stilbenes, benzyl phenyl ethers, tolans and substituted cinnamic acids.
- R 9 and R 10 are different from one another, one of these radicals usually being an alkyl or alkoxy group.
- Other variants of the proposed substituents are common. Many such substances or also mixtures thereof are also commercially available. All these substances can be prepared by methods known from the literature.
- VA, PS-VA, IPS, FFS or PALC mixture according to the invention may also comprise compounds in which, for example, H, N, O, Cl and F have been replaced by the corresponding isotopes.
- liquid-crystal displays corresponds to the usual geometry, as described, for example, in EP-A 0 240 379 .
- the mixtures according to the invention preferably comprise one or more of the compounds shown below.
- liquid-crystal mixtures which can be used in accordance with the invention are prepared in a manner which is conventional per se.
- the desired amount of the components used in lesser amount is dissolved in the components making up the principal constituent, advantageously at elevated temperature. It is also possible to mix solutions of the components in an organic solvent, for example in acetone, chloroform or methanol, and to remove the solvent again, for example by distillation, after mixing.
- the dielectrics may also comprise further additives known to the person skilled in the art and described in the literature, such as, for example, UV absorbers like Tinuvin 770 of Ciba Speciality Chemicals, antioxidants and free-radical scavengers. For example, 0-15% of pleochroic dyes, stabilisers or chiral dopants may be added.
- pleochroic dyes may be added, furthermore conductive salts, preferably ethyldimethyldodecylammonium 4-hexoxybenzoate, tetrabutylammonium tetraphenylboranate or complex salts of crown ethers (cf., for example, Haller et al., Mol. Cryst. Liq. Cryst. Volume 24, pages 249-258 (1973 )) in order to improve the conductivity or substances may be added in order to modify the dielectric anisotropy, the viscosity and/or the alignment of the nematic phases. Substances of this type are described, for example, in DE-A 22 09 127 , 22 40 864 , 23 21 632 , 23 38 281 , 24 50 088 , 26 37 430 and 28 53 728 .
- Table A shows possible dopants which can be added to the mixtures according to the invention. If the mixtures according to the invention comprise a dopant, it is generally added in amounts of 0.01 to 4.0% by weight, preferably 0.1 to 1.0% by weight.
- Stabilisers which can be added, for example, to the mixtures according to the invention are shown below in Table B.
- the display used for measurement of the threshold voltage has two plane-parallel outer plates at a separation of 20 ⁇ m and electrode layers with overlying alignment layers of SE-1211 (Nissan Chemicals) on the insides of the outer plates, which effect a homeotropic alignment of the liquid crystals.
- CY-3-02 17.00 % Clearing point [°C]: 80.0 CY-5-02 8.00 % ⁇ n [589 nm, 20°C]: 0.0908 CCY-3-02 9.00 % ⁇ [kHz, 20°C]: -3.8 CCY-4-02 9.00 % ⁇ ⁇ [kHz, 20°C]: 3.9 CCY-5-02 7.00 % ⁇ ⁇ [kHz, 20°C]: 7.7 CPY-2-02 7.00 % CPY-3-02 9.00 % CC-3-V 32.00 % CCQU-3-F 2.00 %
- CY-3-02 17.00 % Clearing point [°C]: 80.5 CY-5-02 8.00 % ⁇ n [589 nm, 20°C]: 0.0910 CCY-3-02 9.00 % ⁇ [kHz, 20°C]: -3.8 CCY4-02 9.00 % ⁇ ⁇ [kHz, 20°C]: 3.9 CCY-5-02 8.00 % ⁇ ⁇ [kHz, 20°C]: 7.7 CPY-2-02 7.00 % CPY-3-02 8.00 % CC-3-V 28.00 % CCH-34 4.50 % CGU-3-F 1.50 %
- Example 7a (Host) Example 7b CY-3-02 17.00 % PGU-2-F 7.00 % CY-5-02 8.00 % PGU-3-F 10.00 % CCY-3-02 9.00 % PUQU-3-F 8.00 % CCY-3-03 9.00 % CC-3-V1 9.00 % CCY-4-02 7.00 % CC-3-V 39.00 % CPY-2-02 8.00 % CCP-V-1 6.00 % CPY-3-02 8.00 % CCP-V2-1 7.00 % CC-3-V 24.00 % CCGU-3-F 2.00 % CH-34 5.00 % CBC-33 2.00 % CCH-35 5.00 % PGP-2-3 5.00 % PGP-2-4 5.00 % Clearing point [°C]: 80.5 ⁇ n [589 nm, 20°C]: 0.0892 Clearing point [°C]: 74.5 ⁇ [kHz, 20°C]: -4.0 ⁇ n [
- Example 7b Bigger ⁇ ⁇ and ⁇ ⁇ values are obtained by adding mixture of Example 7b having a positive ⁇ into the host mixture of Example 7a: 93 % of Mixture of Example 7a (Host) + 7 % of Mixture of Example 7b: Clearing point [°C]: 80.0 ⁇ n [589 nm, 20°C]: 0.091 ⁇ [kHz, 20°C]: -3.3 ⁇ ⁇ [kHz, 20°C]: 3.9 ⁇ ⁇ [kHz, 20°C]: 7.3
- CY-3-02 10.00 % Clearing point [°C]: 81.0 CCY-3-02 10.50 % ⁇ n [589 nm, 20°C]: 0.0909 CCY-4-02 9.00 % ⁇ [kHz, 20°C]: -3.6 CPY-2-02 9.00 % ⁇ ⁇ [kHz, 20°C]: 4.7 CPY-3-02 9.00 % ⁇ ⁇ [kHz, 20°C]: 8.3 CC-3-V 29.00 % CCP-3F.F.F 5.00 % PCH-301 4.50 % CK-3-F 3.00 % CK-4-F 8.00 % CK-5-F 3.00 %
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Abstract
Description
-
- R0, R1, R2 and R1*
- each, independently of one another, denote H, an alkyl or alkenyl radical having up to 15 C atoms which is unsubstituted, monosubstituted by CN or CF3 or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in these radicals may be replaced by -O-, -S-,
- A1, A1*, A2*
- each, independently of each other
- a) denote a 1,4-cyclohexenylene or 1,4-cyclohexylene radical, in which one or two non-adjacent CH2 groups may be replaced by -O- or -S-,
- b) denote a 1,4-phenylene radical, in which one or two CH groups may be replaced by N,
- c) denote a radical from the group consisting of piperidine- 1,4-diyl-, 1,4-bicyclo[2.2.2]octylene-, naphthalene-2,6- diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydro- naphthalene-2,6-diyl, phenanthrene-2,7-diyl and fluorene-2,7-diyl,
- Z1, Z1* and Z2*
- each, independently of one another denote -CO-O-, -O-CO-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CH2CH2-, -(CH2)4-, -C2F4-, -CH2CF2-, -CF2CH2-, -CF=CF-, -CH=CF-, -CF=CH-, -CH=CH-, -C≡C- or a single bond,
- m and m*
- each independently of one another denote 0, 1 or 2
- p
- denotes 1 or 2
- q
- denotes 0 or 1
- v
- denotes 1 to 6
- L1* and L2*
- each independently of one another denote H or F
- X1 and X2
- each independently of one another denote, F, Cl, CHF2, CF3, OCHF2 or OCF3
- Q
- single bond, -CF2-, -CHF-, -OCF2- or -OCHF- and
- Y
- F or Cl.
- Media of this type are to be used, in particular, for electro-optical displays with active-matrix addressing based on the ECB effect, for IPS (in plane switching) and for FFS (fringe field switching) displays.
- The principle of electrically controlled birefringence, the ECB (electrically controlled birefringence) effect or DAP (deformation of aligned phases) effect was described for the first time in 1971 (M.F. Schieckel and K. Fahrenschon, "Deformation of nematic liquid crystals with vertical orientation in electrical fields", Appl. Phys. Lett. 19 (1971), 3912). Papers by J.F. Kahn (Appl. Phys. Lett. 20 (1972), 1193) and G. Labrunie and J. Robert (J. Appl. Phys. 44 (1973), 4869) followed.
- The papers by J. Robert and F. Clerc (SID 80 Digest Techn. Papers (1980), 30), J. Duchene (Displays 7 (1986), 3) and H. Schad (SID 82 Digest Techn. Papers (1982), 244) have shown that liquid-crystalline phases must have high values for the ratio between the elastic constants K3/K1, high values for the optical anisotropy Δn and values for the dielectric anisotropy Δε of -0.5 to -5 in order to be suitable for use in high-information display elements based on the ECB effect. Electro-optical display elements based on the ECB effect have a homeotropic edge alignment. Dielectrically negative liquid-crystal media can also be used in displays which use the so-called IPS effect.
- Industrial application of this effect in electro-optical display elements requires LC phases which have to satisfy a multiplicity of requirements. Particularly important here are chemical resistance to moisture, air and physical influences, such as heat, radiation in the infrared, visible and ultraviolet regions, and direct and alternating electric fields.
- Furthermore, LC phases which can be used industrially are required to have a liquid-crystalline mesophase in a suitable temperature range and low viscosity.
- None of the series of compounds having a liquid-crystalline mesophase that have been disclosed hitherto includes a single compound which meets all these requirements. Mixtures of two to 25, preferably three to 18, compounds are therefore generally prepared in order to obtain substances which can be used as LC phases. However, it has not been possible to prepare optimum phases easily in this manner, since no liquid-crystal materials having significantly negative dielectric anisotropy and adequate long-term stability have hitherto been available.
- Matrix liquid-crystal displays (MLC displays) are known. Non-linear elements which can be used for individual switching of the individual pixels are, for example, active elements (i.e. transistors). The term "active matrix" is then used, where a distinction can be made between two types:
- 1. MOS (metal oxide semiconductor) transistors on a silicon wafer as substrate.
- 2. Thin-film transistors (TFTs) on a glass plate as substrate.
- In type 1, the electro-optical effect used is usually dynamic scattering or the guest-host effect. The use of single-crystal silicon as substrate material restricts the display size, since even modular assembly of various part-displays results in problems at the joins.
- In the case of the more promising type 2, which is preferred, the electro-optical effect used is usually the TN effect.
- A distinction is made between two technologies: TFTs comprising compound semiconductors, such as, for example, CdSe, or TFTs based on polycrystalline or amorphous silicon. The latter technology is being worked on intensively worldwide.
- The TFT matrix is applied to the inside of one glass plate of the display, while the other glass plate carries the transparent counterelectrode on its inside. Compared with the size of the pixel electrode, the TFT is very small and has virtually no adverse effect on the image. This technology can also be extended to fully colour-compatible displays, in which a mosaic of red, green and blue filters is arranged in such a way that a filter element is opposite each switchable pixel.
- The TFT displays disclosed hitherto usually operate as TN cells with crossed polarisers in transmission and are back-lit.
- The term MLC displays here covers any matrix display with integrated non-linear elements, i.e. besides the active matrix, also displays with passive elements, such as varistors or diodes (MIM = metal-insulator-metal).
- MLC displays of this type are particularly suitable for TV applications (for example pocket TVs) or for high-information displays in automobile or aircraft construction. Besides problems regarding the angle dependence of the contrast and the response times, difficulties also arise in MLC displays due to insufficiently high specific resistance of the liquid-crystal mixtures [TOGASHI, S., SEKIGUCHI, K., TANABE, H., YAMAMOTO, E., SORIMACHI, K., TAJIMA, E., WATANABE, H., SHIMIZU, H., Proc. Eurodisplay 84, Sept. 1984: A 210-288 Matrix LCD Controlled by Double Stage Diode Rings, pp. 141 ff., Paris; STROMER, M., Proc. Eurodisplay 84, Sept. 1984: Design of Thin Film Transistors for Matrix Addressing of Television Liquid Crystal Displays, pp. 145 ff., Paris]. With decreasing resistance, the contrast of an MLC display deteriorates. Since the specific resistance of the liquid-crystal mixture generally drops over the life of an MLC display owing to interaction with the inside surfaces of the display, a high (initial) resistance is very important for displays that have to have acceptable resistance values over a long operating period.
- The disadvantage of the MLC-TN displays disclosed hitherto is due to their comparatively low contrast, the relatively high viewing-angle dependence and the difficulty of producing grey shades in these displays.
- There thus continues to be a great demand for MLC displays having very high specific resistance at the same time as a wide operating-temperature range, short response times and low threshold voltage with the aid of which various grey shades can be produced.
- The invention has the object of providing MLC displays which are based on the ECB, IPS or FFS effect and do not have the disadvantages indicated above, or only do so to a lesser extent, and at the same time have very high specific resistance values.
- It has now been found that this object can be achieved if nematic liquid-crystal mixtures which contain at least one compound of the formula I, IIA and/or IIB and at least one compound of the formula I* are used in these display elements. By adding small amounts of compounds of the formula I* having a positive Δε value to a host having a negative Δε value, the values for ε∥ and ε⊥ can be controlled which is important for the capacitance of LC mixtures, especially for VA mixtures.
- The invention thus relates to a liquid-crystalline medium having negative dielectric anisotropy which contains at least one compound selected from the group of compounds of the formula I, IIA and IIB and at least one compound of the formula I*.
- Mixtures for IPS and VA applications containing compounds of the formula I are known for example from
WO 2004/048500 . The components of the formulae I*, IIA and/or IIB are disclosed for example inWO91/03450 EP 0 364 538 ,EP 0 363 458 andDE 39 06 058 . - LC mixtures having positive Δε for TN-TFT applications containing < 35 % compounds having negative Δε values are known from
U.S. 6,929,832 . - Further LC mixtures are known from
EP 0 949 232 A1 ,US 2004/0245500 A1 ,EP 0 969 071 A1 , andJP 2005 298733 US 7,306,831 B1 ). - By the use of compounds of the formulae I, IIA and/or IIB having a negative dielectrically anisotropy (Δε) in combination with small amounts of compounds of the formula I* having a positive dielectrically anisotropy, the values for ε⊥ and ε∥ can be controlled, especially for LC mixtures for VA, PS-VA, IPS, PALC and FFS applications.
- The mixtures according to the invention exhibit very favourable values for the capacitive threshold, relatively high values for the holding ratio and at the same time very good low-temperature stability as well as very low rotational viscosities.
- Some preferred embodiments are indicated below:
a) Liquid-crystalline medium contains one or more, preferably 1, 2 or 3, compound(s) of the formulae I and one or more, preferably one, compound(s) of the formula I*.
In the compounds of the formula I R1 is preferably alkyl; m is preferably 1; Z' is preferably a single bond. R0 is preferably H. A1 is preferably a 1,4-cyclohexenylene or 1,4-cyclohexylene radical, in which one or two non-adjacent CH2 groups may be replaced by -O-.
b) Liquid-crystalline medium contains one or more compounds of the formula IIA and/or IIB and one or more, preferably one, compound(s) of the formula I*.
In the compounds of the formula IIA and/or IIB X1 is preferably F or Cl and X2 is preferably F.
c) Liquid-crystalline medium which additionally contains one or more compounds of the formula III - R31 and R32
- each, independently of one another, denote a straight- chain alkyl, alkylalkoxy, alkenyl, alkenyloxy or alkoxy radical having up to 12 C atoms, and
- alkyl and alkyl*
- each, independently of one another, denote a straight- chain alkyl radical having 1-6 C atoms, and
- alkenyl and alkenyl*
- each, independently of one another, denote a straight- chain alkenyl radical having 2-6 C atoms.
- R7 and R8
- each, independently of one another, have one of the meaning indicated for R1 in Claim 1, and
- w and x
- each, independently of one another, denote 1 to 6.
- Especially preferred embodiments are given in the following:
- The mixture according to the invention contains one compound of the formula I and one compound of the formula I*-1a.
- The mixture according to the invention contains two or three compounds of the formula I and one compound of the formula I*-1a.
- The mixture according to the invention contains a compound of the formula IIB in combination with a compound of the formula I*-1a and/or I*-1b.
- The mixture according to the invention contains at least one compound of the formula I, IIA and IIB in combination with at least one compound of the formula I*-4a, and/or I*-7b and/or I*-9a and/or I*-10a and/or I*-11a.
- The mixture according to the invention contains at least one compound of the formula IIB in combination with at least one compound of the formula I*-2a and/or I*-3a and/or I*-5a and/or I*-6a.
- The invention furthermore relates to an electro-optical display with active-matrix addressing based on the ECB effect, characterised in that it contains, as dielectric, a liquid-crystalline medium according to one of Claims 1 to 16.
- The liquid-crystal mixture preferably has a nematic phase range of at least 60 K and a flow viscosity ν20 of at most 30 mm2 · s-1 at 20°C.
- The liquid-crystal mixture according to the invention has a Δε of -0.5 to -8.0, preferably -2.0 to -7.0, in particular -3.0 to -6.0, where Δε denotes the dielectric anisotropy. The rotational viscosity γ1 is preferably < 150 mPa·s, in particular < 140 mPa·s.
- The birefringence Δn in the liquid-crystal mixture is generally between 0.07 and 0.16, preferably between 0.08 and 0.11.
- The mixtures according to the invention are suitable for all VA-TFT applications, such as, for example, MVA, PVA and ASV. They are furthermore suitable for PS-VA (Polymer stabilized VA), IPS, FFS and PALC applications with negative Δε.
- The individual components of the formulae I, I*, IIA, IIB and III of the liquid-crystal phases according to the invention are either known or their methods of preparation can easily be derived from the prior art by the person skilled in the relevant art since they are based on standard methods described in the literature.
- The nematic liquid-crystal mixtures in the displays according to the invention generally comprise two components A and B, which themselves consist of one or more individual compounds.
- Component A has significantly negative dielectric anisotropy and gives the nematic phase a dielectric anisotropy of ≤ -0.3. It preferably comprises compounds of the formulae I, IIA and/or IIB.
- The proportion of component A is preferably between 45 and 100 %, in particular between 60 and 100 %.
- For component A, one (or more) individual compound(s) which has (have) a value of Δε of s -0.8 is (are) preferably selected. This value must be more negative the smaller the proportion A in the mixture as a whole.
- Component B has pronounced nematogeneity and a flow viscosity of not greater than 30 mm2 · s-1, preferably not greater than 25 mm2 · s-1, at 20°C.
- Particularly preferred individual compounds in component B are extremely low-viscosity nematic liquid crystals having a flow viscosity of not greater than 18 mm2 · s-1, preferably not greater than 12 mm2 · s-1, at 20°C.
- Component B is monotropically or enantiotropically nematic, has in most cases no smectic phases and is able to prevent the occurrence of smectic phases down to very low temperatures in liquid-crystal mixtures. Some compounds of Component B have smectic phases but their solubility are usually good. For example, if various materials of high nematogeneity are added to a smectic liquid-crystal mixture, the nematogeneity of these materials can be compared through the degree of suppression of smectic phases that is achieved.
-
- R51 and R52
- each, independently of one another, have the meanings given for R31 and R32, and
- Particular preference is given to compounds of the formula III. Preferred compounds of the formulae V and VI are given in the following table for example CCP-V-m, CCP-Vn-m, CCP-nOm, CCP-nm, BCH-nm.
- In addition, these liquid-crystal phases may also comprise more than 18 components, preferably 18 to 25 components.
- The phases preferably comprise 4 to 15, in particular 5 to 12, compounds of the formulae I, IIA and/or IIB and optionally compounds of the formulae III-VI, preferably compounds of the formula III and V.
- Besides compounds of the formulae I, I*, IIA and/or IIB and III, other constituents may also be present, for example in an amount of up to 45% of the mixture as a whole, but preferably up to 35 %, in particular up to 10 %.
- The other constituents are preferably selected from nematic or nematogenic substances, in particular known substances, from the classes of the azoxybenzenes, benzylideneanilines, biphenyls, terphenyls, phenyl or cyclohexyl benzoates, phenyl or cyclohexyl cyclohexanecarboxylates, phenylcyclohexanes, cyclohexylbiphenyls, cyclohexylcyclohexanes, cyclohexylnaphthalenes, 1,4-biscyclohexylbiphenyls or cyclohexylpyrimidines, phenyl- or cyclohexyldioxanes, optionally halogenated stilbenes, benzyl phenyl ethers, tolans and substituted cinnamic acids.
- The most important compounds which are suitable as constituents of liquid-crystal phases of this type can be characterised by the formula IV
R9-L-G-E-R10 IV
in which L and E each denote a carbocyclic or heterocyclic ring system from the group formed by 1,4-disubstituted benzene and cyclohexane rings, 4,4'-disubstituted biphenyl, phenylcyclohexane and cyclohexylcyclohexane systems, 2,5- disubstituted pyrimidine and 1,3-dioxane rings, 2,6-disubstituted naphthalene, di- and tetrahydronaphthalene, quinazoline and tetrahydroquinazoline,
G is-CH=CH- -N(O)=N- -CH-CQ- -CH=N(O)- -C≡C- -CH2-CH2- -CO-O- -CH2-O- -CO-S- -CH2-S- -CH=N- -COO-Phe-COO- -CF2O- -CF=CF- -OCF2 -OCH2- -(CH2)4- -(CH2)3O- - In most of these compounds, R9 and R10 are different from one another, one of these radicals usually being an alkyl or alkoxy group. Other variants of the proposed substituents are common. Many such substances or also mixtures thereof are also commercially available. All these substances can be prepared by methods known from the literature.
- It goes without saying for the person skilled in the art that the VA, PS-VA, IPS, FFS or PALC mixture according to the invention may also comprise compounds in which, for example, H, N, O, Cl and F have been replaced by the corresponding isotopes.
- The construction of the liquid-crystal displays according to the invention corresponds to the usual geometry, as described, for example, in
EP-A 0 240 379 . - The following examples are intended to explain the invention without limiting it. Above and below, percentages are per cent by weight; all temperatures are indicated in degrees Celsius.
- Besides the compounds of the formulae I, IIA, IIB and I*, the mixtures according to the invention preferably comprise one or more of the compounds shown below.
-
- The liquid-crystal mixtures which can be used in accordance with the invention are prepared in a manner which is conventional per se. In general, the desired amount of the components used in lesser amount is dissolved in the components making up the principal constituent, advantageously at elevated temperature. It is also possible to mix solutions of the components in an organic solvent, for example in acetone, chloroform or methanol, and to remove the solvent again, for example by distillation, after mixing.
- The dielectrics may also comprise further additives known to the person skilled in the art and described in the literature, such as, for example, UV absorbers like Tinuvin 770 of Ciba Speciality Chemicals, antioxidants and free-radical scavengers. For example, 0-15% of pleochroic dyes, stabilisers or chiral dopants may be added.
- For example, 0-15% of pleochroic dyes may be added, furthermore conductive salts, preferably ethyldimethyldodecylammonium 4-hexoxybenzoate, tetrabutylammonium tetraphenylboranate or complex salts of crown ethers (cf., for example, Haller et al., Mol. Cryst. Liq. Cryst. Volume 24, pages 249-258 (1973)) in order to improve the conductivity or substances may be added in order to modify the dielectric anisotropy, the viscosity and/or the alignment of the nematic phases. Substances of this type are described, for example, in
DE-A 22 09 127 ,22 40 864 ,23 21 632 ,23 38 281 ,24 50 088 ,26 37 430 and28 53 728 . -
-
- The following examples are intended to explain the invention without limiting it. Above and below,
- Vo
- denotes the threshold voltage, capacitive [V] at 20°C
- Δn
- denotes the optical anisotropy measured at 20°C and 589 nm
- Δε
- denotes the dielectric anisotropy at 20°C and 1 kHz
- cp.
- denotes the clearing point [°C]
- γ1
- denotes the rotational viscosity measured at 20°C [mPa·s]
- LTS
- denotes the low temperature stability, determined in test cells and/or in the bulk state
- For the purposes of the present invention, all concentrations are, unless explicitly stated otherwise, indicated in per cent by weight and relate to the corresponding mixture or mixture component. All physical properties are and have been determined in accordance with "Merck Liquid Crystals, Physical Properties of Liquid Crystals", Status Nov. 1997, Merck KGaA, Germany, and apply to a temperature of 20°C, unless explicitly stated otherwise. The rotational viscosity is determined by the rotating permanent magnet method or by the transient current method and the flow viscosity in a modified Ubbelohde viscometer.
- The display used for measurement of the threshold voltage has two plane-parallel outer plates at a separation of 20 µm and electrode layers with overlying alignment layers of SE-1211 (Nissan Chemicals) on the insides of the outer plates, which effect a homeotropic alignment of the liquid crystals.
-
CY-5-O2 5.00% Clearing point [°C]: 80.0 CCY-3-O2 9.00% Δn [589 nm, 20°C]: 0.0917 CCY-3-O3 5.00% ε∥ [1 kHz, 20°C]: 4.3 CPY-2-O2 11.00% ε⊥ [1 kHz, 20°C]: 7.0 CPY-3-O2 12.00% Δε [1 kHz, 20°C]: -3.4 CCH-34 9.00% K1 [20°C]: 12.9 CCH-301 8.00% K3 [20°C]: 3.5 CC-3-V 15.00% γ1 [mPa·s, 20°C]: 117 PCH-301 9.00 % V0[V] 2.04 4.00% 6.00% 4.00% CCP-3F.F.F 3.00% -
CY-3-02 18.00 % Clearing point [°C]: 80.5 CY-5-02 6.50 % Δn [589 nm, 20°C]: 0.0905 CCY-3-02 11.00 % Δε [kHz, 20°C]: -3.9 CCY-4-02 10.00 % ε∥ [kHz, 20°C]: 3.9 CCY-5-02 7.00 % ∥⊥ [kHz, 20°C]: 7.8 CPY-2-02 5.00 % CPY-3-02 9.00 % CC-3-V 32.50 % PUQU-3-F 1.00 % -
CY-3-02 17.00 % Clearing point [°C]: 80.0 CY-5-02 8.00 % Δn [589 nm, 20°C]: 0.0908 CCY-3-02 9.00 % Δε [kHz, 20°C]: -3.8 CCY-4-02 9.00 % ε∥ [kHz, 20°C]: 3.9 CCY-5-02 7.00 % ε⊥ [kHz, 20°C]: 7.7 CPY-2-02 7.00 % CPY-3-02 9.00 % CC-3-V 32.00 % CCQU-3-F 2.00 % -
CY-3-02 17.00 % Clearing point [°C]: 80.5 CY-5-02 8.00 % Δn [589 nm, 20°C]: 0.0910 CCY-3-02 9.00 % Δε [kHz, 20°C]: -3.8 CCY4-02 9.00 % ε∥ [kHz, 20°C]: 3.9 CCY-5-02 8.00 % ε⊥ [kHz, 20°C]: 7.7 CPY-2-02 7.00 % CPY-3-02 8.00 % CC-3-V 28.00 % CCH-34 4.50 % CGU-3-F 1.50 % -
CY-3-02 18.00 % Clearing point [°C]: 80.0 CY-5-02 3.00 % Δn [589 nm, 20°C]: 0.0912 CCY-3-02 11.00 % Δε [kHz, 20°C]: -3.3 CCY-3-03 3.00 % ε∥ [kHz, 20°C]: 4.0 CCY-4-02 9.00 % ε⊥ [kHz, 20°C]: 7.3 CPY-2-02 9.00 % CPY-3-02 9.00 % CC-3-V 34.50 % CCP-3F.F.F 3.50 % -
CY-3-02 13.00 % Clearing point [°C]: 81.0 CCY-3-02 12.00% Δn [589 nm, 20°C]: 0.0909 CCY-3-03 7.50 % Δε [kHz, 20°C]: -3.3 CPY-2-02 9.00 % ε∥ [kHz, 20°C]: 4.0 CPY-3-02 6.00 % ε⊥ [kHz, 20°C]: 7.3 CCH-34 5.50 % CC-3-V 31.00 % CK-3-F 4.00 % CK-4-F 4.00 % PYP-2-3 3.00 % CCG-V-F 5.00 % -
Example 7a (Host) Example 7b CY-3-02 17.00 % PGU-2-F 7.00 % CY-5-02 8.00 % PGU-3-F 10.00 % CCY-3-02 9.00 % PUQU-3-F 8.00 % CCY-3-03 9.00 % CC-3-V1 9.00 % CCY-4-02 7.00 % CC-3-V 39.00 % CPY-2-02 8.00 % CCP-V-1 6.00 % CPY-3-02 8.00 % CCP-V2-1 7.00 % CC-3-V 24.00 % CCGU-3-F 2.00 % CH-34 5.00 % CBC-33 2.00 % CCH-35 5.00 % PGP-2-3 5.00 % PGP-2-4 5.00 % Clearing point [°C]: 80.5 Δn [589 nm, 20°C]: 0.0892 Clearing point [°C]: 74.5 Δε [kHz, 20°C]: -4.0 Δn [589 nm, 20°C]: 0.1154 ε∥ [kHz, 20°C]: 3.6 Δε [kHz, 20°C]: -5.3 ε⊥: [kHz, 20°C]: 7.7 ε∥ [kHz, 20°C]: 8.3 ε⊥ [kHz, 20°C]: 3.1 K1 [20°C:] 13.00 γ1 [mPa·s, 20 °C]: 58.00 - Bigger ε∥ and ε⊥ values are obtained by adding mixture of Example 7b having a positive Δε into the host mixture of Example 7a:
93 % of Mixture of Example 7a (Host) + 7 % of Mixture of Example 7b:Clearing point [°C]: 80.0 Δn [589 nm, 20°C]: 0.091 Δε [kHz, 20°C]: -3.3 ε∥ [kHz, 20°C]: 3.9 ε⊥ [kHz, 20°C]: 7.3 -
CY-3-02 18.00 % Clearing point [°C]: 80.0 CY-5-02 7.00 % Δn [589 nm, 20°C]: 0.0901 CCY-3-02 9.00 % Δε [kHz, 20°C]: -4.0 CCY-3-03 6.00 % ε∥ [kHz, 20°C]: 3.6 CCY-4-02 7.00 % ε⊥ [kHz, 20°C]: 7.6 CPY-2-02 9.00 % CPY-3-02 9.00 % CC-3-V 13.00 % CCH-34 8.00 % CCH-35 8.00 % CCH-301 4.00 % - 94 % of Mixture of Example 8a (Host) + 6 % of Mixture of Example 7b:
Clearing point [°C]: 80.0 Δn [589 nm, 20°C]: 0.0912 Δε [kHz, 20°C]: -3.4 ε∥ [kHz, 20°C]: 3.9 ε⊥ [kHz, 20°C]: 7.3 -
CY-3-02 19.00 % Clearing point [°C]: 81.5 CY-5-02 5.00 % Δn [589 nm, 20°C]: 0.0915 CCY-3-02 10.00 % Δε [kHz, 20°C]: -3.4 CCY-4-02 9.00 % ε∥ [kHz, 20°C]: 3.9 CPY-2-02 10.00 % ε⊥ [kHz, 20°C]: 7.3 CPY-3-02 9.00 % CC-3-V 17.00 % CCP-3F.F.F 3.50 % CCH-34 9.00 % CCH-35 8.50 % -
CY-3-02 18.00 % Clearing point [°C]: 80.0 CY-5-02 3.00 % Δn [589 nm, 20°C]: 0.0912 CCY-3-02 11.00 % Δε [kHz, 20°C]: -3.3 CCY-3-03 3.00 % ε∥ [kHz, 20°C]: 4.0 CCY-4-02 9.00 % ε⊥ [kHz, 20°C]: 7.3 CPY-2-02 9.00 % CPY-3-02 9.00 % CC-3-V 34.50 % CCP-3F.F.F 3.50 % -
CY-3-02 20.00 % Cleaning point [°C]: 80.0 CY-5-02 6.50 % Δn [589 nm, 20°C]: 0.0912 CCY-3-02 12.00 % Δε [kHz, 20°C]: -3.6 CCY-4-02 10.00 % ε∥ [kHz, 20°C]: 4.3 CCY-5-02 3.50 % ε⊥ [kHz, 20°C]: 7.9 CPY-2-02 4.50 % CPY-3-02 10.00 % CC-3-V 28.50 % CCP-3F.F.F 5.00 % -
CY-3-02 18.00 % Clearing point [°C]: 80.5 CY-5-02 11.00 % Δn [589 nm, 20°C]: 0.0913 CCY-3-02 12.00 % Δε [kHz, 20°C]: -3.6 CCY-4-02 9.00 % ε∥ [kHz, 20°C]: 4.6 CCY-5-02 6.00 % ε⊥ [kHz, 20°C]: 8.2 CPY-2-02 3.50 % CPY-3-02 9.00 % CC-3-V 24.50 % CCP-3F.F.F 7.00 % -
CY-3-02 10.00 % Clearing point [°C]: 81.0 CCY-3-02 10.50 % Δn [589 nm, 20°C]: 0.0909 CCY-4-02 9.00 % Δε [kHz, 20°C]: -3.6 CPY-2-02 9.00 % ε∥ [kHz, 20°C]: 4.7 CPY-3-02 9.00 % ε⊥ [kHz, 20°C]: 8.3 CC-3-V 29.00 % CCP-3F.F.F 5.00 % PCH-301 4.50 % CK-3-F 3.00 % CK-4-F 8.00 % CK-5-F 3.00 %
d) Liquid-crystalline medium contains one, two, three, four or more, preferably one, two or three compounds of the formula I.
e) Liquid-crystalline medium contains one compound of the formula I*.
f) Liquid-crystalline medium in which R1 in the formula I preferably has the following meanings: straight-chain alkyl, vinyl, 1 E-alkenyl or 3-alkenyl.
If R1 denotes alkenyl, it is preferably CH2=CH, CH3-CH=CH, C3H, CH=CH, CH2=CH-C2H4 or CH3-CH=CH-C2H4.
R0 preferably denotes H or straight-chain alkyl having 1 to 6 C atoms, in particular methyl, ethyl or propyl. Especially R0 denotes H.
If A1 and Z1 in formula I are present twice, in the case that m=2, A1 and Z1 can have the same or different meanings.
g) Liquid-crystalline medium in which the proportion of compounds of the formula I in the mixture as a whole is at least 5% by weight, preferably at least 10 % by weight.
h) Liquid-crystalline medium in which the proportion of compounds of the formulae IIA and/or IIB in the mixture as a whole is at least 10 % by weight, preferably ≥ 20 % by weight.
i) Liquid-crystalline medium in which the proportion the compounds of the formula III in the mixture as a whole is at least 5 % by weight, preferably ≥ 10 % by weight.
j) Liquid-crystalline medium which contains at least one compound selected from the sub-formulae I1 to I18
Particularly preferred media contain one or more compounds selected from the group consisting of the compounds of the formulae Ia to Ih
Particular preference is given to media which contain at least one compound of the formula Ia and/or lh. Especially preferred mixtures contain one, two or three compounds of the formula Ia.
k) Liquid-crystalline medium which contains at least one compound selected from the sub-formulae IIA-1 to IIA-24
CH2CH2CH=CHCH3. Especially preferred are the compounds of the formulae IIA-1, IIA-2, IIA-3, IIA-4, IIA-5, IIA-6, IIA-17, IIA-19 and IIA-21.
In the compounds of the formula IIA X1 and X2 preferably are both F.
l) Liquid-crystalline medium which contains at least one compound selected from the sub-formulae IIB-1 to IIB-4
In the compounds of the formula IIB X1 and X2 preferably are both F.
m) Liquid-crystalline medium which additionally contains a compound selected from the formulae IIIa to IIIf
Particularly preferred compounds of the formulae IIIe and IIIf are indicated below:
n) Liquid-crystalline medium which contains
5-30 % by weight | of one or more compounds of the formulae I and one or more compounds of the formula I* |
or | |
20-70 % by weight | of one or more compounds selected from the formulae IIA and/or IIB and one or more compounds of the formula I* |
or | |
10-100 % by weight | of one or more compounds of the formulae I, one or more compounds selected from the formulae IIA and/or IIB and one or more compounds of the formula I* |
o) Liquid-crystalline medium which additionally contains one or more tetracyclic compounds of the formulae
p) Liquid-crystalline medium which additionally contains one or more compounds of the formulae V-1 to V-17
Preferred mixtures contain at least one compound of the formulae V-16 and/or V-17.
q) Liquid-crystalline medium additionally contains one or more compounds of the formulae T-1 to T-3
Especially preferred are compounds of the formula T-3. Preferred compounds of the formula T-3 are the compounds of the formulae T-3a and T-3b
r) Liquid-crystalline medium which contains at least one compound selected from the sub-formulae I*-1 to I*-11,
L3* and L4* each independently denote H or F.
Particularly preferred media contain one or more compounds selected from the compounds of the formula I* wherein L1* and L2* are both F.
Especially preferred are compounds of the formulae I*-1a, I*-1b, I*-2a, I*-3a, I*-4a, I*-5a, I*-6a, I*-7a, I*-7b, I*-8a, I*-9a, I*-10a, I*-11a
alkyl and alkenyl have the meanings as given above.
Preferred mixtures contain ≤ 10 %, especially ≤ 5 %, most preferred ≤ 3 % by weight of the compounds of the formula I*.
Claims (17)
- Liquid-crystalline medium based on a mixture of polar compounds having negative dielectric anisotropy (Δε), characterized in that it contains at least one compound selected from the group of compounds of the formula I, IIA and IIBR0, R1, R2 and R1* each, independently of one another, denote H, an alkyl or alkenyl radical having up to 15 C atoms which is unsubstituted, monosubstituted by CN or CF3 or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in these radicals may be replaced by -O-, -S-,A1, A1*, A2* each, independently of each othera) denote a 1,4-cyclohexenylene or 1,4-cyclohexylene radical, in which one or two non-adjacent CH2 groups may be replaced by -O- or -S-,b) denote a 1,4-phenylene radical, in which one or two CH groups may be replaced by N,c) denote a radical from the group consisting of piperidine- 1,4-diyl-, 1,4-bicyclo[2.2.2]octylene-, naphthalene-2,6- diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydro- naphthalene-2,6-diyl, phenanthrene-2,7-diyl and fluorene-2,7-diyl, where the radicals a), b) and c) may be mono- or polysubstituted by halogen atoms,Z1, Z1* and Z2* each, independently of one another denote -CO-O-, -O-CO-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CH2CH2-, -(CH2)4-, -C2F4-, -CH2CF2-, -CF2CH2-, -CF=CF-, -CH=CF-, -CF=CH-, -CH=CH-, -C≡C- or a single bond, andm and m* each independently of one another denote 0, 1 or 2p denotes 1 or 2q denotes 0 or 1v denotes 1 to 6L1* and L2* each independently of one another denote H or FX1 and X2 each independently of one another denote, F, Cl, CHF2, CF3, OCHF2 or OCF3Q single bond, -CF2-, -CHF-, -OCF2- or -OCHF- andY F or Cl.
- Liquid crystalline medium according to any of Claims 1 to 3, characterised in that L1* is F and L2* is H or F.
- Liquid crystalline medium according to any of Claims 1 to 4, characterised in that L1* = L2* = F.
- Liquid-crystalline medium according to any of Claims 1 or 5, characterised in that R0 denotes H.
- Liquid-crystalline medium according to any of Claims 1 to 6, characterised in that it contains at least one compound of the formula I1.
- Liquid-crystalline medium according to any of Claims 1 to 9, characterised in that it additionally contains one or more compounds of the formula III
- Liquid-crystalline medium according to any of Claims 1 to 10, characterised in that it contains one, two, three, four or more compounds of the formulae I, IIA and/or IIB.
- Liquid-crystalline medium according to any of Claims 1 to 11, characterised in that the proportion of compounds of the formula I in the mixture as a whole is at least 5 % by weight.
- Liquid-crystalline medium according to any of Claims 1 to 12, characterised in that the proportion of compounds of the formula I* in the mixture as a whole is ≤ 10 % by weight.
- Liquid-crystalline medium according to any of Claims 1 to 13, characterised in that the proportion of compounds of the formulae IIA and/or IIB in the mixture as a whole is at least 20 % by weight.
- Liquid-crystalline medium according to any of Claims 1 to 14, characterised in that the proportion of compounds of the formula III in the mixture as a whole is at least 5 % by weight.
- Liquid-crystalline medium which contains
5-30 % by weight of one or more compounds of the formulae I and one or more compounds of the formula I* or 20-70 % by weight of one or more compounds selected from the formula IIA and/or IIB and one or more compounds of the formula I* or 10-100 % by weight of one or more compounds of the formulae I, one or more compounds selected from the formula IIA and/or IIB and one or more compounds of the formula I* - Electro-optical display with active-matrix addressing based on the ECB, VA, PS-VA, PALC, IPS or FFS effect, characterised in that it contains, as dielectric, a liquid-crystalline medium according to one of Claims 1 to 16.
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PCT/EP2008/003962 WO2008138643A1 (en) | 2007-05-16 | 2008-05-16 | Liquid- crystalline medium |
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EP (1) | EP2144975B1 (en) |
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EP2292720A1 (en) * | 2009-09-08 | 2011-03-09 | Merck Patent GmbH | Liquid-crystal display |
EP2514800B2 (en) * | 2011-04-21 | 2018-03-07 | Merck Patent GmbH | Compounds and liquid crystalline medium |
CN102559201B (en) * | 2011-12-23 | 2013-12-11 | 陕西师范大学 | Allyloxy lateral multi-fluoric liquid crystal compound and preparation method thereof |
GB201301786D0 (en) * | 2012-02-15 | 2013-03-20 | Merck Patent Gmbh | Liquid-crystalline medium |
KR20140001071A (en) * | 2012-06-25 | 2014-01-06 | 한양대학교 산학협력단 | Liquid crystal compound |
TWI609069B (en) * | 2012-09-24 | 2017-12-21 | 捷恩智股份有限公司 | Liquid crystal display element, and liquid crystal composition and use thereof |
US9695361B2 (en) | 2012-10-05 | 2017-07-04 | Dic Corporation | Liquid crystal composition and liquid crystal display element using the same |
CN103254907B (en) * | 2013-04-23 | 2016-01-20 | 石家庄诚志永华显示材料有限公司 | Negative dielectric anisotropy liquid crystal composition |
US9933679B2 (en) | 2013-07-17 | 2018-04-03 | Lc Vision, Llc | Birefringence improving agent, ferroelectric liquid crystal composition and liquid crystal display device using the agent, and compound |
JP6428637B2 (en) | 2013-10-31 | 2018-11-28 | 日本ゼオン株式会社 | Polymerizable compound, polymerizable composition, polymer, and optical anisotropic body |
CN109072079B (en) * | 2016-11-22 | 2020-02-14 | Dic株式会社 | Liquid crystal composition and liquid crystal display element |
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KR100215373B1 (en) * | 1989-09-06 | 1999-08-16 | 플레믹 크리스티안 | Fluorobenzene derivatives and liquid-crystalline medium |
US6458433B1 (en) * | 1996-12-16 | 2002-10-01 | Chisso Corporation | Difluorophenyl derivatives, liquid-crystal compounds, and liquid-crystal composition |
JP4320824B2 (en) * | 1998-06-02 | 2009-08-26 | チッソ株式会社 | Alkenyl compound having negative value of Δε, liquid crystal composition, and liquid crystal display device |
US6929832B2 (en) | 1999-03-03 | 2005-08-16 | Merck Patent Gmbh | Liquid-crystal medium, and electro-optical display containing the liquid-crystal medium |
DE50308195D1 (en) * | 2002-11-22 | 2007-10-25 | Merck Patent Gmbh | LIQUID CRYSTALLINE MEDIUM |
DE102004006669A1 (en) * | 2003-03-06 | 2004-09-16 | Merck Patent Gmbh | Liquid crystal medium, useful in liquid crystal displays, is based on a mixture of polar compounds having a positive dielectric anisotropy and contains at least one difluorinated aryl compound and at least one fluorinated aryl compound |
JP2005298733A (en) * | 2004-04-14 | 2005-10-27 | Chisso Corp | Liquid crystal composition and liquid crystal display element |
US7815979B2 (en) * | 2006-04-04 | 2010-10-19 | Samsung Electronics Co., Ltd. | Liquid crystal composition and liquid crystal display including same |
EP1958999B1 (en) * | 2007-02-13 | 2012-07-11 | Merck Patent GmbH | Liquid crystalline medium |
-
2008
- 2008-05-16 WO PCT/EP2008/003962 patent/WO2008138643A1/en active Application Filing
- 2008-05-16 US US12/600,083 patent/US20100301270A1/en not_active Abandoned
- 2008-05-16 DE DE602008003216T patent/DE602008003216D1/en active Active
- 2008-05-16 EP EP08758588A patent/EP2144975B1/en not_active Not-in-force
- 2008-05-16 KR KR1020097026144A patent/KR101473507B1/en active IP Right Grant
- 2008-05-16 AT AT08758588T patent/ATE486114T1/en not_active IP Right Cessation
Also Published As
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ATE486114T1 (en) | 2010-11-15 |
WO2008138643A1 (en) | 2008-11-20 |
WO2008138643A8 (en) | 2009-02-05 |
EP2144975A1 (en) | 2010-01-20 |
KR20100017812A (en) | 2010-02-16 |
US20100301270A1 (en) | 2010-12-02 |
DE602008003216D1 (en) | 2010-12-09 |
KR101473507B1 (en) | 2014-12-17 |
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